CN101648912B - Continuous preparation method of 4-nitro-3,5-dimethylpyridine-N-oxide - Google Patents
Continuous preparation method of 4-nitro-3,5-dimethylpyridine-N-oxide Download PDFInfo
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Abstract
The invention discloses a continuous preparation method of 4-nitro-3,5-dimethylpyridine-N-oxide, and the method comprises the following steps: adopting 3,5-dimethylpyridine as raw material to perform oxidation and nitrification and obtaining 4-nitro-3,5-dimethylpyridine-N-oxide. The purity of the product obtained in the invention is high, the separation and purification methods are simple, the dosage of organic solvent is low, the environmental pollution is little, the cost is less, thus the method of the invention is applicable to continuous industrial production.
Description
Technical field:
The invention belongs to pharmacy field, be specifically related to a kind of 4-nitro-3, the preparation method of 5-lutidine-N-oxide compound.The present invention is from 3; The oxidation of 5-lutidine, the nitrated 4-nitro-3 that directly obtains, 5-lutidine-N-oxide compound need be after oxidation extract with organic solvent and obtains the oxynitride solid; And directly descend the step nitration reaction, make two-step reaction can realize serialization.
Background technology:
3, the 5-lutidine is important organic synthesis raw material, introduces the N-oxide groups on the pyridine ring and can improve its nitrated response capacity, changes the direction of nitro attack simultaneously.Because the negative charge of oxygen has suitable major part to return in the pyridine ring through conjugative effect in the N-oxide compound pyridine molecule, it is pi-conjugated to form p-, therefore is activated, and nitro is mainly gone up in the 2-position of N-oxy picolinate ring and 4-position.
Prepare 4-nitro-3 at present, the method for 5-lutidine-N-oxide compound has: select for use various catalyst oxidation alkyl pyridines to obtain pyridine-N-oxide, carry out nitration reaction with the oxynitride solid again and generate 4-nitro-3,5-lutidine-N-oxide compound.Also need extract for intermediate product, the not only organic solvent of labor, and extraction is incomplete, causes a large amount of wastes of intermediate product.
Summary of the invention
The purpose of this invention is to provide a kind of serialization and prepare 4-nitro-3, the method for 5-lutidine-N-oxide compound, the inventive method make and oxidation, nitrated formation serialization make industrial production be achieved.
The objective of the invention is through following scheme implementation:
-kind of a serialization prepares 4-nitro-3, and the method for 5-lutidine-N-oxide compound is characterized in that 3; 5-lutidine heat temperature raising to 40 ℃～90 ℃ time adds oxygenant in two batches, add oxygenant for the first time after; When continuing to be heated to solution temperature and reaching 80 ℃～100 ℃, insulation reaction 1～6 hour is cooled to 40 ℃～90 ℃ then; Add the oxygenant oxidation again, when continuing to be heated to solution temperature and reaching 80 ℃～100 ℃, reacted 12～16 hours; Underpressure distillation goes out most of water then, be cooled to room temperature after, heat again, when being heated to 40 ℃～110 ℃, dripping nitrating agent and carry out nitratedly, reaction is spent the night.
The present invention selects for use nitrating agent to be generally the mixture of nitric acid and vitriolic mixing acid, nitric acid and organic solvent or the mixture of nitric acid and acetic anhydride, preferred oil of mirbane of organic solvent and toluene.Nitric acid shared weight percentage in mixing acid or mixture is 50%-60%.The nitrated ability of the selected nitrating agent of the present invention not only is enough to nitrated pyridine, and makes raw material nitrated as much as possible fully.Used nitrating agent and 3, the mol ratio of 5-lutidine-N-oxide compound is 1.5～3.5: 1.
Above-mentioned nitration reaction is temperature prioritised to be between 50 ℃～100 ℃.
Select appropriate organic solvent extraction 4-nitro-3 after the nitration reaction, in the time of 5-lutidine-N-oxide compound, reclaim nitrating agent.Organic solvent can be: oil of mirbane, chlorobenzene, toluene, phenols (preferred Wood creosote, thick biphenol), halogenated hydrocarbons (preferred trichloroethane, ethylene dichloride) or isopropyl ether.
The present invention and prior art beneficial effect relatively: the oxidizing reaction technology that the present invention adopts is a kind of adding that does not need solvent Glacial acetic acid min. 99.5 (as catalyzer); And directly adopt oxygenant oxidation 3; The 5-lutidine obtains 3,5-lutidine-N-oxide compound.And the product after the oxidation is cleaning substance H
2O does not influence 3, the 5-lutidine-generation of N-oxide compound, purification; The nitration reaction of then carrying out, step is simple and easy to do, and nitrating agent can also recycle, thereby has solved nitrating agent recycle problem, practices thrift the explained hereafter cost greatly.In addition, the product purity that adopts the inventive method to prepare is high, and separating and purifying method is simple; Reduce the organic solvent usage quantity; The environmental pollution that reduces cost and reduce when removing solvent to be produced has realized the environmental protection chemical technique, is suitable for industry to go up serialization production.
Specific embodiments:
The present invention can be further understood through embodiment, but content of the present invention can not be limited.
Embodiment 1:
To 3, the 5-lutidine carries out oxidation, nitrated, and underpressure distillation obtains 4-nitro-3 after organic solvent extraction, 5-lutidine-N-oxide compound faint yellow solid, and step is following:
In the 500ml four-hole boiling flask, add 3 of 70ml, 5-lutidine (concentration is 96.9%) carries out heat temperature raising to 50 ℃, and adding weight percent concentration according to the dropping mode is 30%H
2O
2, add at twice, at first add the 30%H of 55.5g
2O
2, in 3 hours, add control feed rate 0.1～0.2ml/ second, heated soln then, when temperature reaches 80 ℃, insulation reaction 3 hours; Be cooled to 50 ℃ then, add 33.3g 30%H again
2O
2In 1 hour, add, heated soln, when temperature reaches 100 ℃, insulation reaction 12 hours; Finish through the HPLC detection reaction, and to calculate this moment oxidizing reaction yield be 95.21%, dewater so reaction soln is carried out underpressure distillation, remove 75ml water after; Be heated to solution temperature when reaching 70 ℃, carry out nitration reaction, drip nitrating agent (nitric acid and vitriolic nitration mixture; V/V=1.2: 1) 220ml, drip nitrating agent after, make solution temperature reach 90 ℃ and insulation reaction and spend the night.Product solution extracts through toluene, and organic phase is carried out underpressure distillation to doing, and reclaims toluene, obtains faint yellow solid 4-nitro-3,5-lutidine-N-oxide compound 87.21g, and the nitration reaction yield is 91.84%, HPLC purity is 97.49%.This oxidation, nitrated total recovery are: 87.44%.
Embodiment 2
In the 500ml four-hole boiling flask, add 3 of 70ml, 5-lutidine (concentration is 96.9%) carries out heat temperature raising to 70 ℃; Add the peroxo-phenylformic acid, add at twice, at first add the peroxo-phenylformic acid of 150g according to the dropping mode; Control feed rate 0.1～0.2ml/ second well, in 6 hours, add, then heated soln; When temperature reaches 80 ℃, insulation reaction 6 hours; Be cooled to 40 ℃ then, add the peroxo-phenylformic acid of 80g again, in 1 hour, add heated soln; When temperature reached 80 ℃, insulation reaction 5 hours finished through the HPLC detection reaction; And to calculate this moment oxidizing reaction yield be 96.32%, dewaters so reaction soln is carried out underpressure distillation, remove 75ml water after; Heating is carried out nitration reaction when solution temperature reaches 50 ℃, drip the nitrating agent (mixture of nitric acid and acetic anhydride; V/V=1.2: 1) 211ml, drip nitrating agent after, make solution temperature reach 90 ℃ and insulation reaction and spend the night.Through oil of mirbane the solution of nitration mixture and product is extracted organic phase is carried out underpressure distillation to doing; Reclaim oil of mirbane, obtain faint yellow solid 4-nitro-3,5-lutidine-N-oxide compound 85.32g; The nitration reaction yield is 89.33%, and HPLC purity is 96.01%.This oxidation, nitrated total recovery are: 86.7%.
Embodiment 3
In the 500ml four-hole boiling flask, add 3 of 70ml, 5-lutidine (concentration is 96.9%) carries out heat temperature raising to 80 ℃; Add sodium perborate, add at twice, the sodium perborate that at first adds 60g added in 6 hours; Heated soln then, when temperature reaches 100 ℃, insulation reaction 6 hours; Be cooled to 60 ℃ then, the sodium perborate that adds 35g again added in one hour, heated soln; When temperature reached 90 ℃, insulation reaction 5 hours finished through the HPLC detection reaction; And to calculate this moment oxidizing reaction yield be 97.06%, dewaters so reaction soln is carried out underpressure distillation, remove 75ml water after; Heating is carried out nitration reaction when solution temperature reaches 70 ℃, drip (the mixture of nitric acid and toluene; V/V=1.5: 1) 115ml, drip nitric acid after, make solution temperature reach 90 ℃ and insulation reaction and spend the night.Through Wood creosote the solution of nitration mixture and product is extracted organic phase is carried out underpressure distillation to doing; Reclaim Wood creosote, obtain faint yellow solid 4-nitro-3,5-lutidine-N-oxide compound 85.63g; The nitration reaction yield is 89.66%, and HPLC purity is 97.21%.This oxidation, nitrated total recovery are: 87.02%.
Embodiment 4
In the 500ml four-hole boiling flask, add 3 of 70ml, 5-lutidine (concentration is 96.9%) carries out heat temperature raising to 90 ℃; Add Youxiaolin, add at twice, control feed rate 0.1～0.2ml/ second by continuously a small amount of feeding manner; The Youxiaolin that at first adds 60g added in 6 hours; Heated soln then, when temperature reaches 100 ℃, insulation reaction 6 hours; Be cooled to 90 ℃ then, the Youxiaolin that adds 30g again added in 1 hour, heated soln; When temperature reached 100 ℃, insulation reaction 14 hours finished through the HPLC detection reaction; And to calculate this moment oxidizing reaction yield be 95.51%, dewaters so reaction soln is carried out underpressure distillation, remove 75ml water after; Heating is carried out nitration reaction when solution temperature reaches 70 ℃, drip the nitrating agent (mixture of nitric acid and oil of mirbane; V/V=1.5: 1) 192ml, drip nitrating agent after, make solution temperature reach 90 ℃ and insulation reaction and spend the night.Through ethylene dichloride the solution of product is extracted organic phase is carried out underpressure distillation to doing; Reclaim ethylene dichloride, obtain faint yellow solid 4-nitro-3,5-lutidine-N-oxide compound 87.54g; The nitration reaction yield is 93.14%, and HPLC purity is 96.14%.This oxidation, nitrated total recovery are: 88.96%.
Embodiment 5
In the 500ml four-hole boiling flask, add 3 of 70ml, 5-lutidine (concentration is 96.9%) carries out heat temperature raising to 70 ℃; Add the peroxo-phthalic acid, add at twice, at first add the peroxo-phthalic acid of 150g according to the dropping mode; Control feed rate 0.1～0.2ml/ second well, in 6 hours, add, then heated soln; When temperature reaches 80 ℃, insulation reaction 6 hours; Be cooled to 40 ℃ then, the peroxo-phthalic acid that adds 90g again added heated soln in 1 hour; When temperature reached 80 ℃, insulation reaction 16 hours finished through the HPLC detection reaction; And to calculate this moment oxidizing reaction yield be 95.43%, dewaters so reaction soln is carried out underpressure distillation, remove 75ml water after; Heating is carried out nitration reaction when solution temperature reaches 70 ℃, drip nitrating agent (nitric acid and vitriolic nitration mixture; V/V=1.2: 1) 220ml, drip nitrating agent after, make solution temperature reach 90 ℃ and insulation reaction and spend the night.Through isopropyl ether the solution of nitration mixture and product is extracted organic phase is carried out underpressure distillation to doing; Reclaim isopropyl ether, obtain faint yellow solid 4-nitro-3,5-lutidine-N-oxide compound 86.84g; The nitration reaction yield is 92.47%, and HPLC purity is 97.09%.This oxidation, nitrated total recovery are: 88.25%.
Embodiment 6
In the 500ml four-hole boiling flask, add 3 of 70ml, 5-lutidine (concentration is 96.9%) carries out heat temperature raising to 60 ℃; Adding weight percent concentration is 40% Peracetic Acid, adds at twice by continuously a small amount of feeding manner, and the weight percent concentration that at first adds 1650g is 40% Peracetic Acid; In 4～5 hours, add; Heated soln then, when temperature reaches 90 ℃, insulation reaction 3 hours; Be cooled to 70 ℃ then, the weight percent concentration that adds 800g again is 40% Peracetic Acid, in 2 hours, adds heated soln; When temperature reached 100 ℃, insulation reaction 12 hours finished through the HPLC detection reaction, and calculating oxidizing reaction yield this moment is 98.56%; So reaction soln is carried out underpressure distillation dehydration, be 1.0MPa in vacuum tightness, temperature is carried out underpressure distillation in the time of 60 ℃～100 ℃, remove 75ml water after; Heating when solution temperature reaches 70 ℃, is carried out nitration reaction, drips nitrating agent (nitric acid and vitriolic nitration mixture; V/V=1.2: 1) 220ml, drip nitrating agent after, the heated soln temperature reaches 100 ℃ and insulation reaction and spends the night.Extract through the solution of toluene to product, organic phase is carried out underpressure distillation to doing, obtain faint yellow solid 4-nitro-3,5-lutidine-N-oxide compound 86.75g reclaims toluene.The nitration reaction yield is 89.45%, and detecting purity through HPLC is 96.34%.This oxidation, nitrated total recovery are: 88.16%.Realized the serialization that oxidation, nitration processes are produced.
Embodiment 7
In the 500ml four-hole boiling flask, add 3 of 70ml, 5-lutidine (concentration is 96.9%) carries out heat temperature raising to 60 ℃; Adding weight percent concentration is 40% Peracetic Acid, adds at twice by continuously a small amount of feeding manner, and the weight percent concentration that at first adds 1650g is 40% Peracetic Acid; In 4～5 hours, add; Heated soln then, when temperature reaches 90 ℃, insulation reaction 3 hours; Be cooled to 70 ℃ then, the weight percent concentration that adds 800g again is 40% Peracetic Acid, in 2 hours, adds heated soln; When temperature reached 100 ℃, insulation reaction 16 hours finished through the HPLC detection reaction, and calculating oxidizing reaction yield this moment is 98.56%; So reaction soln is carried out underpressure distillation dehydration, be 1.0MPa in vacuum tightness, temperature is carried out underpressure distillation in the time of 60 ℃～100 ℃, remove water after; Use dichloromethane extraction, merge organic phase, organic phase is dewatered, organic phase is carried out normal pressure or underpressure distillation with anhydrous magnesium sulfate; Reclaim methylene dichloride, get solid 69.3g3,5-lutidine-N-oxide compound white solid; Then carry out nitration reaction again; Add the concentrated sulfuric acid dissolution soild oxide of 50ml, system is heated up, when solution temperature reaches 90 ℃; Drip nitrating agent (nitric acid and vitriolic nitration mixture; V/V=1.2: 1) 220ml, drip nitrating agent after, the heated soln temperature reaches 100 ℃ and insulation reaction and spends the night.With among the NaOH with a large amount of acid, filter out vitriol, again water is carried out extracted in toluene, organic phase is carried out underpressure distillation to doing, obtain faint yellow solid 4-nitro-3,5-lutidine-N-oxide compound 84.35g reclaims toluene.The nitration reaction yield is 89.16%, and thick product is through petroleum ether, and it is 95.34% that HPLC detects purity.This oxidation, nitrated total recovery are: 87.88%.This shows that this technology is in two steps, process is loaded down with trivial details, and with 3,5-lutidine-N-oxide compound is taken out, and has increased the usage quantity of organic solvent dichloromethane, also makes the losing of product; Nitrated back obtains a large amount of acid with the alkali lye neutralization, generates a large amount of abraum salts, is unfavorable for environmental protection; Neutralize the vitriol oil, increase cost as solvent, uneconomical.
Claims (8)
1. 4-nitro-3, the continuous preparation method of 5-lutidine-N-oxide compound is characterized in that this method is with 3; 5-lutidine heat temperature raising to 40 ℃～90 ℃ time adds oxygenant in two batches, add oxygenant for the first time after; When continuing to be heated to solution temperature and reaching 80 ℃～100 ℃, insulation reaction 1～6 hour is cooled to 40 ℃～90 ℃ then; Add oxygenant again, when continuing to be heated to solution temperature and reaching 80 ℃～100 ℃, insulation reaction 12～16 hours; Underpressure distillation goes out most of water then, be cooled to room temperature after, heat again, when being heated to 40 ℃～110 ℃, dripping nitrating agent and carry out nitratedly, reaction is spent the night.
2. according to the said preparation of claim 1 4-nitro-3, the method for 5-lutidine-N-oxide compound is characterized in that used nitrating agent is the mixture of nitric acid and vitriolic mixing acid, nitric acid and organic solvent or the mixture of nitric acid and acetic anhydride.
3. according to the said preparation of claim 2 4-nitro-3, the method for 5-lutidine-N-oxide compound is characterized in that used organic solvent is oil of mirbane or toluene.
4. according to the said preparation of claim 1 4-nitro-3, the method for 5-lutidine-N-oxide compound is characterized in that used nitrating agent and 3, and the mol ratio of 5-lutidine-N-oxide compound is 1.5～3.5: 1.
5. according to the said preparation of claim 1 4-nitro-3, the method for 5-lutidine-N-oxide compound is characterized in that described nitration reaction temperature is 50 ℃～100 ℃.
6. according to the said preparation of claim 1 4-nitro-3, the method for 5-lutidine-N-oxide compound is characterized in that, adopts organic solvent extraction 4-nitro-3 after the nitration reaction, and 5-lutidine-N-oxide compound reclaims nitrating agent simultaneously.
7. according to the said preparation of claim 6 4-nitro-3, the method for 5-lutidine-N-oxide compound is characterized in that described organic solvent is oil of mirbane, toluene, phenols, halogenated hydrocarbons or isopropyl ether.
8. according to the said preparation of claim 7 4-nitro-3, the method for 5-lutidine-N-oxide compound is characterized in that described phenols is Wood creosote or thick biphenol, and halogenated hydrocarbons is trichloroethane or ethylene dichloride.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0103553B1 (en) * | 1982-08-26 | 1989-02-22 | Aktiebolaget Hässle | Intermediates for the preparation of omeprazole |
| DE3840372A1 (en) * | 1988-11-15 | 1990-05-31 | Lentia Gmbh | METHOD FOR THE PRODUCTION OF 3,5-DIMETHYL-4-METHOXYPYRIDINE DERIVATIVES AND A NEW INTERMEDIATE PRODUCT THEREFOR |
-
2009
- 2009-09-14 CN CN2009100350146A patent/CN101648912B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0103553B1 (en) * | 1982-08-26 | 1989-02-22 | Aktiebolaget Hässle | Intermediates for the preparation of omeprazole |
| DE3840372A1 (en) * | 1988-11-15 | 1990-05-31 | Lentia Gmbh | METHOD FOR THE PRODUCTION OF 3,5-DIMETHYL-4-METHOXYPYRIDINE DERIVATIVES AND A NEW INTERMEDIATE PRODUCT THEREFOR |
| CN1042705A (en) * | 1988-11-15 | 1990-06-06 | Cl药物股份公司 | 3,5-dimethyl-4-methoxypyridine derivatization method and be used for the novel intermediate product of this method for making |
Non-Patent Citations (2)
| Title |
|---|
| 李祖文等.3 5-二甲基-4-甲氧基-2-氯甲基吡啶的合成.《山西化工》.2005 |
| 李祖文等.3,5-二甲基-4-甲氧基-2-氯甲基吡啶的合成.《山西化工》.2005,第25卷(第4期),9-10. * |
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